CN100406506C - Diene rubber composition and process for producing the same - Google Patents

Abstract

A diene rubber composition with excellent processability which reconciles fuel-saving performance with high road-holding performance and is excellent in tensile strength and wearing resistance; a diene rubber obtained by crosslinking the composition; and a process for producing the composition. The composition is characterized in that it comprises 100 parts by weight of a diene rubber having a molecular-weight distribution, which is represented by the ratio of the weight-average molecular weight to the number-average molecular weight, of 1.1 to 30, 20 to 200 parts by weight of silica, and a cationic polymer and that the amount of rubber components insoluble in toluene is 0.2 to 1 g per g of the silica. The process for producing the composition is characterized by reacting a rubber latex stabilized with an anionic emulsifying agent with an aqueous silica suspension containing a cationic polymer and co-coagulating the rubber contained in the rubber latex and the silica contained in the aqueous suspension in a specific pH range.

Description

Diene rubber composition and manufacture method thereof

Technical field

The present invention relates to new diene rubber composition and manufacture method thereof, in more detail, the invention provides and a kind ofly can access tensile strength and good cross-linked rubber and good diene rubber composition, this cross-linked rubber and the manufacture method thereof of shaping processability of wear resistant.

Background technology

Past as the reinforcement filler of rubber, is extensive use of carbon black and silicon-dioxide, in general, extensively uses kneading devices such as Banbury, opening rubber mixing machine, kneading machine to be coupled to drying process (being also referred to as dry mix) in the rubber.

In recent years, fill the diene rubber composition of silicon-dioxide, compare with carbon black-filled rubber combination, not only can be free painted, low in the pollution of the environment, antiseize quality is good, and can have both low oil consumption and high road surface tack [グ リ Star プ], is gazed at elastomeric material as tire tread.

Yet the surface of silicon-dioxide is covered by the silanol base, has very strong self coagulation, and therefore, the affinity of shortage and diene series rubber is difficult to be scattered in the rubber well.Therefore, adopt drying process to fill the diene rubber composition of silicon-dioxide, compare, have the problem that adds the epistasis variation of the tensile strength of the cross-linked rubber that obtains by cross-linking and wear resistant etc. with carbon black-filled rubber combination.

Therefore, in order to improve the affinity of diene series rubber and silicon-dioxide, the someone has proposed to cooperate silane coupling agent and has adopted method (with reference to document 1 is arranged earlier) that drying process fills, uses to have imported and have with the specialty elastomer of the functional group of the affinity of silicon-dioxide and adopt method (with reference to document 2 is arranged earlier) that drying process fills etc.

But, the composition that adopts aforesaid method to obtain, insufficient to the improvement of the affinity of silicon-dioxide and diene series rubber, silicon-dioxide to rubber add epistasis to improve effect insufficient.

In general, index as the affinity that is used to observe rubber and silicon-dioxide, have that to be determined at toluene etc. be the method for the amount of insoluble rubber constituent in the good solvent (below be also referred to as bound rubber) to rubber, owing to reason such as the affinity of silicon-dioxide and rubber is low, can distinguish, in above-mentioned composition, the amount of this bound rubber is very low.

On the other hand, in the drying process, method as the amount that increases above-mentioned bound rubber, someone has proposed to use by making 3 kinds of special specialty elastomers that monomer copolymerization obtains, it is mixed with silicon-dioxide, thereby contained the method (with reference to document 3 is arranged earlier) of the rubber combination of bound rubber in a large number.

But, employed specialty elastomer in the above-mentioned rubber combination is according to its manufacture method, with the narrow molecular weight distribution of weight-average molecular weight to the ratio of number-average molecular weight (below be also referred to as Mw/Mn) expression, be below 1.0～1.1, therefore aspect processibility and versatility, also have the leeway of improvement.

Opposite with above-mentioned drying process, the somebody has proposed make silicon dioxide granule and rubber particles that the aqueous liquid dispersion with silicon-dioxide mixes, disperses and form with rubber latex and has solidified simultaneously, obtains uniform coagulative so-called ``

For example, adopt the aqueous liquid dispersion of the silicon-dioxide of median size below 1 μ m of handling with a large amount of cationic high-moleculars is mixed with rubber latex, the rubber combination (reference has document 4 earlier) that method that above-mentioned rubber and silicon-dioxide solidify is altogether obtained by interpolation salt; By the aqueous liquid dispersion of the silicon-dioxide of handling with silane coupling agent is mixed with rubber latex, to wherein interpolation is sour, the rubber combination (reference has document 5 earlier) that method that rubber and silicon-dioxide solidify is altogether obtained is known.These have earlier in the document, and the amount of the bound rubber of rubber combination does not illustrate.

But, the rubber combination that aforesaid method obtains, according to present inventor's affirmation, bound rubber is with respect to the amount of silicon-dioxide, and with respect to silica 1 g, bound rubber is just very many more than 1g.Like this, the rubber combination that the amount of bound rubber is many, when in the cross-linked rubber that obtains by cross-linking, using silicon-dioxide, as the low oil consumption of its advantage and high road surface tack to improve effect little, and exist rubber combination itself and become really up to the mark, even mixing problem that can not the gelatinous resultant of destructive etc. takes place easily, still there is room for improvement in mixing processibility aspect.

In addition, the somebody has proposed to mix with rubber latex and to wherein adding the method that organic ionic compound solidifies rubber and silicon-dioxide altogether (with reference to document 6 is arranged earlier) by the aqueous liquid dispersion with silicon-dioxide, but as can be seen by the comparative example described later that uses aforesaid method, the co-coagulate that adopts this method to obtain can not get the sufficient affinity of silicon-dioxide and rubber, and the growing amount of bound rubber is few.

And then, somebody's proposition is by mixing rubber latex the method (with reference to document 7 is arranged earlier) that rubber and silicon-dioxide are solidified altogether with the waterborne suspension of the silicon-dioxide that contains acrylamide-copolymer of dimethylaminoethyl methacrylate, but have in the document earlier above-mentioned, the amount of bound rubber is record not, and, occasion using usually the acrylamide-dimethylaminoethyl methacrylate that uses as flocculation agent is difficult to generate fully bound rubber.

As mentioned above, molecular weight distribution wide, be combined with in the composition of silicon-dioxide in the general diene series rubber as SBR etc., nobody proposes can bring into play the rubber combination that contains bound rubber in right amount of good rerum natura so far.

(document 1 is arranged earlier) spy opens flat 3-252431 communique

(document 2 is arranged earlier) special public clear 63-2886 communique

(document 3 is arranged earlier) spy opens flat 7-118449 communique

(document 4 is arranged earlier) spy opens the 2001-213971 communique

(document 5 is arranged earlier) spy opens flat 10-231381 communique

No. 3,122,518, (document 6 is arranged earlier) USP

No. 4,366,285, (document 7 is arranged earlier) USP

Summary of the invention

Therefore, the objective of the invention is to, a kind of diene rubber composition that contains silicon-dioxide is provided, this composition is in the composition of wide diene series rubber of molecular weight distribution and silicon-dioxide, contains bound rubber with specific amount, not only can have low oil consumption and high road surface tack concurrently, and the favorable dispersity of silicon-dioxide, can obtain having the good tensile strength and the cross-linked rubber of wear resistant, and, even when being shaped, also demonstrate good processibility.

The inventor etc. have carried out deep research in order to solve above-mentioned technical task.Its result, by moderately containing bound rubber with inaccessible amount traditionally with respect to silicon-dioxide, successfully obtain a kind of like this diene rubber composition, and the cross-linked rubber that obtain crosslinked by this composition (following will be called " diolefin series cross-linked rubber " by the crosslinked cross-linked rubber that obtains of diene rubber composition simply) has good tensile strength and wear resistant, simultaneously, processibility during shaping is also good, so far finishes the present invention.

Promptly, the invention provides a kind of diene rubber composition, it is characterized in that, comprising that weight-average molecular weight is 1.1～30 diene series rubber 100 weight parts, silicon-dioxide 20～200 weight parts and cationic high-molecular to the molecular weight distribution of the ratio (Mw/Mn) of number-average molecular weight expression, is 0.2～1g with respect to the amount of the rubber constituent that is insoluble to toluene of silica 1 g.

Should illustrate, in the present invention, " being insoluble to the rubber constituent of toluene ", be that bound rubber is meant at the uncrosslinked rubber combination that will be mixed with weighting agent and during with the toluene extracting, is not extracted and residual rubber constituent.Detailed condition is shown in the embodiment described later.

In addition, the present invention also provides a kind of and is combined with linking agent and silane coupling agent and gives the bridging property diene rubber composition of bridging property and with the crosslinked diolefin series cross-linked rubber that forms of this bridging property diene rubber composition in above-mentioned diene rubber composition.

And then, the present invention also provides a kind of manufacture method of diene rubber composition, it is characterized in that, as the manufacture method of can industry making above-mentioned diene rubber composition, use diene series rubber, silicon-dioxide and cationic high-molecular with specific ratio, adopt specific method that it is solidified altogether simultaneously.

Promptly, the invention provides a kind of manufacture method of diene rubber composition, it is characterized in that, silicon-dioxide and cationic high-molecular are mixed in water, obtain aqueous liquid dispersion, be that 1.1～30 diene series rubber latex mixes then with this aqueous liquid dispersion and the molecular weight distribution of the ratio of number-average molecular weight being represented according to weight-average molecular weight, silicon-dioxide and rubber are solidified altogether after, with co-coagulate dehydration, drying.

Embodiment

(diene series rubber)

In the present invention, the above-mentioned Mw/Mn of diene series rubber is that 1.1～30, particularly 1.2～20, more especially 1.4～15 known diene series rubber can use with being not particularly limited.

In the occasion of the diene series rubber that uses Mw/Mn less than 1.1, the processibility reduction of the bridging property rubber combination that obtains when mixing and when shaping, and also the wear resistant of diolefin series cross-linked rubber reduces.In addition, when Mw/Mn surpasses 30, the diolefin series cross-linked rubber, particularly reduction such as low oil consumption when the tire purposes and rigidity.

In addition, the weight-average molecular weight (Mw) as diene series rubber of the present invention is preferably 5,000～2,000,000, and more preferably 50,000～1,500,000, be preferably 100,000～1,200,000 especially.The occasion of diene series rubber that has the weight-average molecular weight of above-mentioned scope in use, in the diolefin series cross-linked rubber that obtains by the present invention, the balance that adds epistasis of low oil consumption and wear resistant etc. is good.

Mix the occasion of using at the diene series rubber with multiple different molecular weight, Mw/Mn is often big than original Mw/Mn separately, even but in this occasion, also preferably be in the scope of the present invention's regulation.

The shape of molecular weight distribution, being the elution curve of the diene series rubber of gel permeation chromatography, can be unimodality, also can be multimodality.

Diene series rubber with above-mentioned Mw/Mn has no particular limits, and can adopt known emulsion polymerization or solution polymerization process to make.Among the present invention, preferably use those by conjugate diene monomer or conjugate diene monomer and can with the monomer of this conjugate diene monomer copolymerization diene series rubber by the letex polymerization manufactured.This emulsion polymerisation process can adopt known condition.

Extending oil as using when polymer latex is reclaimed as rubber can use normally used those oil in rubber industry, can list the petroleum line softener, department of botany's tenderizer, lipid acid of alkane hydrocarbon system, fragrant family, cycloalkanes hydrocarbon system etc.In the occasion of petroleum line softener, the content of preferred Ppolynuclear aromatic is lower than 3%.This content adopts the method (inspection method of the The Institute Petroleum of Britain) of IP346 to measure.

As above-mentioned conjugative monomer, can list for example 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-butadiene, chlorbutadiene, 1,3-pentadiene etc.Wherein, preferred 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, more preferably 1,3-butadiene.These conjugate diene monomers can be used alone or in combination of two or more kinds respectively.

In addition, can have no particular limits with the monomer of this conjugate diene monomer copolymerization.For example, can list and contain amino vinyl monomer, the vinyl monomer that contains pyridyl, the vinyl monomer that contains hydroxyl, the vinyl monomer that contains alkoxyl group, aromatic vinyl monomer etc., wherein, the optimization aromatic vinyl monomer.As aromatic vinyl monomer, can list for example vinylbenzene, alpha-methyl styrene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 2,4-di-isopropyl vinylbenzene, 2,4-dimethyl styrene, 4-t-butyl styrene, the 5-tertiary butyl-2-methyl styrene, monochlorostyrene, dichlorostyrene, phenyl-monofluoride ethene, N, N-dimethyl aminoethyl vinylbenzene, N, N-diethylamino ethyl styrene etc.Wherein, special optimization styrene.These copolymerisable monomers can be used alone or in combination of two or more kinds respectively.

Among the present invention, if the example diene series rubber that can preferably use particularly, can list natural rubber, synthetic polyisoprene, divinyl rubber, styrene butadiene copolymer rubber, chlorine piperylene rubber, isobutylene-isoprene copolymer rubber, acrylonitrile-butadiene copolymer rubber, styrene butadiene-isoprene copolymer rubber, butadiene-isoprene copolymer glue, acrylonitrile-styrene-butadiene copolymer rubber etc.In addition, can also use the modified rubber of functional groups such as importing hydroxyl, carboxyl, alkoxysilyl, amino, epoxy group(ing).

These diene series rubbers can be used alone or in combination of two or more kinds respectively.

Among the present invention, particularly use and contain the more preferably styrene butadiene copolymer rubber of 20～50 weight % of styrene units 1～60 weight %, preferred 10～55 weight %, because the wear resistant of the cross-linked rubber that finally obtains and the balance of road surface tack are good, are preferred therefore.

In addition, the mooney viscosity of above-mentioned diene series rubber (ML1+4,100 ℃) is preferably 10～200, is preferably 30～150 scope especially.

(silicon-dioxide)

In the present invention, the silicon-dioxide that is added in the rubber as weighting agent can use with being not particularly limited.For example, can list method by making silicate base and mineral acid carry out neutralization reaction silicon-dioxide is separated out, be the sedimentation silicon-dioxide of so-called damp process manufacturing, the dry type silicon-dioxide that silicon tetrachloride is burnt obtain in oxyhydrogen flame, with the alkoxide of silicon such as tetramethoxy-silicane and the tetraethoxysilane sol-gel method silicon-dioxide that obtains etc. that in acid or alkaline water-containing organic solvent, is hydrolyzed.In addition, as sedimentation silicon-dioxide, in damp process, also can use Tai-Ace S 150 to make it carry out neutralization reaction and the sedimentation silicon-dioxide that contains metal-salt in a large number that obtains as part or all of mineral acid.

According to the present invention, in above-mentioned silicon-dioxide, the sedimentation silicon-dioxide that adds epistasis, highly productive of preferred rubber.

About above-mentioned sedimentation silicon-dioxide, in more detail, the specific surface area (S that adopts the nitrogen adsorption method to record _BET) be preferably 70～300m ²/ g, more preferably 80～280m ²/ g most preferably is 90～260m ²/ g.

In addition, the specific surface area (S that the absorption of cetyl trimethylammonium bromide (CTAB) is recorded by above-mentioned silicon-dioxide _CTAB) be preferably 60～300m ²/ g, more preferably 70～280m ²/ g most preferably is 80～260m ²/ g.

And then the dibutyl phthalate oil number of above-mentioned silicon-dioxide (the following oil number that also is called simply) is preferably 100～400ml/100g, and more preferably 110～350ml/100g most preferably is 120～300ml/100g.

Diene rubber composition of the present invention with respect to diene series rubber 100 weight parts, contains 20～200 weight parts, preferred 30～150 weight parts, the more preferably silicon-dioxide of 40～120 weight parts.The loading level of above-mentioned silicon-dioxide is lower than the occasion of 20 weight parts, in diene rubber composition that obtains and diolefin series cross-linked rubber, tensile strength and wear resistant etc. add epistasis to improve effect little, if and surpass 200 weight parts, then diene rubber composition becomes really up to the mark, and mixing processibility worsens.

According to the present invention, have the occasion of silicon-dioxide of specific surface area, the oil number of above-mentioned scope in use, the epistasis that adds of the tensile strength of diolefin series cross-linked rubber and wear resistant etc. becomes good especially.

(cationic high-molecular)

Among the present invention, cationic high-molecular is that a kind of to generate bound rubber necessary in order moderately to adjust the affinity of silicon-dioxide and rubber, make in the diene rubber composition that obtains amount with appropriateness.

Above-mentioned cationic high-molecular can not have any polymer that restrictedly uses those ionization to take place and show cationic when being dissolved in the water.For example, representative is that those have primary on its high polymer main chain or side chain, the polymer of amino or its quaternary ammonium salt base of secondary, uncle.

As above-mentioned cationic high-molecular, for example, preferably have primary by making, secondary, uncle is amino or its ammonium salt base, and the polymer that obtains of the monomer polymerization of quaternary ammonium salt base.And then, also can be in the scope that does not suppress above-mentioned effect, the multipolymer that forms with other monomer copolymerizations.

Among the present invention, particularly have the polymer that uncle's monomer polymerization amino and quaternary ammonium salt base obtains by making, make the diene rubber composition that obtains add epistasis become good aspect, be preferred.

Example preferred cation type polymer particularly, can list polymine, polyvinylamine, polyvinylpyridine, the polyamine sulfone, PAH, the polydiene propyl methylamine, polyamide-based amine, the polyacrylate and amino alkyl ester, the polymethyl acrylic acid aminoalkyl ester, poly-aminoalkyl group acrylamide, poly-epoxy group(ing) amine, the polyamide-based polyamines, the polyester polyamines, two cyaniding diamide formaldehyde condensation products, polyalkylene polyamine two cyaniding diamide condensess, epichlorohydrin amine condenses etc., and their ammonium salt, also has diallyl dimethyl ammoniumchloride, the polymer with quaternary ammonium salt base of polymethacrylate methyl chloride etc.

Wherein, preferred polydiene propyl methylamine and ammonium salt thereof, epichlorohydrin amine condenses, diallyl dimethyl ammoniumchloride.

In addition, the weight-average molecular weight of above-mentioned cationic high-molecular is preferably 1,000～1, and 000,000, more preferably 2,000～900,000, most preferably be 3,000～800,000.By making above-mentioned weight-average molecular weight, can improve the effect of improving that adds epistasis of the tensile strength of diolefin series cross-linked rubber and wear resistant etc. more than 1,000, and, by making above-mentioned weight-average molecular weight 1,000, below 000, can make the dispersion of silicon-dioxide in rubber become good.

In addition, the value of the cation equivalent molecular weight of above-mentioned cationic high-molecular is preferably below 220, more preferably below 200, most preferably below 180.

(usage quantity of cationic high-molecular)

In the diene rubber composition of the present invention, the usage quantity of above-mentioned cationic high-molecular, for the growing amount of bound rubber is easily adjusted in the scope of above-mentioned appropriateness, with respect to silica 1 00 weight part, to make cationic high-molecular be 0.1～7.5 weight part, be preferably 0.5～7 weight part, the ratio of 1～6 weight part more preferably.

Promptly, the usage quantity of above-mentioned cationic high-molecular is lower than the occasion of 0.1 weight part, in manufacture method described later, is difficult to generate bound rubber in the diene rubber composition, the amount of bound rubber reduces, and the epistasis that adds of the tensile strength of diolefin series cross-linked rubber and wear resistant etc. has the tendency that reduces.In addition,, the growing amount of bound rubber is too increased, therefore cause the mixing processibility of diolefin series cross-linked rubber and the tendency that oil consumption has reduction if the usage quantity of cationic high-molecular surpasses 7.5 weight parts.And then, when diene series rubber latex and silicon-dioxide are solidified altogether, if the usage quantity of above-mentioned cationic high-molecular is too much, then can make a part of rubber not sneak in the silicon-dioxide but unilaterally solidify, this often causes the distribution of the silicon-dioxide in the rubber to produce inhomogeneous.

Especially, among the present invention,, preferably use the specific surface area (S of above-mentioned silicon-dioxide in the occasion of paying attention to processibility and oil consumption _CTAB) be 80～200m ²The silicon-dioxide of/g.In this occasion, preferably adjust the usage quantity of cationic high-molecular, so that make the specific surface area (unit: m that adopts cetyl trimethylammonium bromide (CTAB) absorption method to record when above-mentioned silicon-dioxide ²/ g) as S, (unit: during weight part) as c, above-mentioned cationic high-molecular can satisfy following relational expression with respect to the use level of above-mentioned silica 1 00 weight part above-mentioned cationic high-molecular.

27≤(S/c)≤70

Promptly, present inventors are in a series of research about diene rubber composition, obtain a kind of like this experience, promptly, for the affinity that makes silicon-dioxide and rubber improves, moderately generate bound rubber, the use level of cationic high-molecular is important, and the use level that it is best and the specific surface area of employed silicon-dioxide have specific relation.So, based on this empirical discovery, if cooperate the cationic high-molecular of optimum quantity, even if do not use or cooperate silane coupling agent etc. slightly, the processibility of the rubber combination that obtains is reduced, silicon-dioxide can be distributed in this rubber combination well.

(bound rubber)

The maximum of diene rubber composition of the present invention is characterised in that in the system of above-mentioned diene series rubber and silicon-dioxide, the amount of bound rubber with respect to silica 1 g, is 0.20～1.0g, is preferably 0.30～0.90g, more preferably 0.35～0.80g.

The amount of above-mentioned bound rubber, yardstick as the dispersiveness of the weighting agent that is used for estimating rubber uses, as mentioned above, in the composition of filling silicon-dioxide in the wide diene series rubber of the molecular weight distribution resembling general diene series rubber and forming, the composition that bound rubber is generated in the scope of appropriateness is that the present invention at first provides.

Like this, by the amount of above-mentioned bound rubber is adjusted to above-mentioned scope, in the time of can providing uncrosslinked have excellent moldability and also the crosslinked cross-linked rubber that obtains has been given play to good rerum naturas such as tensile strength, wear resistant, have diene rubber composition by the inaccessiable good effect of diene rubber composition in the past.

Therefore, the amount of above-mentioned bound rubber, occasion with respect to the not enough 0.20g of silica 1 g, the tensile strength of diolefin series cross-linked rubber and wear resistant etc. add epistasis to improve effect little, if and above 1.0g, then the processibility of diene rubber composition worsens, simultaneously, the diolefin series cross-linked rubber is used for the occasion of tire, and the effect of improving of its low oil consumption and high road surface tack reduces.

About in diene rubber composition of the present invention, the amount of bound rubber is in the mechanism in the above-mentioned scope, and present inventors are presumed as follows.Promptly, adopt manufacture method described later to make on the surface of cationic high-molecular attached to silicon-dioxide, size according to its molecular weight, not densely with the surface coverage of silicon-dioxide, can give affinity to the appropriateness of rubber, can control the growing amount of bound rubber thus, and, according to the specific surface area of the usage quantity of cationic high-molecular and employed silicon-dioxide and particle diameter etc., control the growing amount of bound rubber, can obtain having the diene rubber composition of bound rubber by the measurer of hope.

In contrast, use the composition of above-mentioned record in the patent documentation 3 of the silicon-dioxide that silane coupling agent was handled, cover silica sphere densely by silane coupling agent, be difficult to control the growing amount of bound rubber, and, the composition of record in the patent documentation 4 of the silicon-dioxide of use below the 1 μ m that cationic high-molecular was handled, the particle diameter of silicon-dioxide is little, be difficult to control the growing amount of bound rubber, simultaneously, the quantitative change of the bound rubber in the diene rubber composition that obtains gets extremely many, can not reach purpose of the present invention.

But diene rubber composition of the present invention is not to negate the merging use of silane coupling agent fully, but is generated the existence that governable range content is permitted this silane coupling agent that is reflected at of bound rubber by cationic high-molecular.The amount of this silane coupling agent usually, with respect to silica 1 00 weight part, is below 5 weight parts, is preferably especially below 3 weight parts.

In the diene rubber composition of the present invention, cooperate linking agent to make the bridging property rubber combination, after its processing that is shaped, carry out crosslinkedly, can make the diolefin series cross-linked rubber.

(bridging property rubber combination)

The compound method of bridging property rubber combination of the present invention has no particular limits, and implements to get final product according to ordinary method.For example, in diene rubber composition of the present invention, the Synergist S-421 95 that cooperates the weighting agent, linking agent, crosslinking accelerator, activator of crosslinking, antiaging agent, activator, process oil, softening agent, lubricant, weighting agent etc. of silane coupling agent, carbon black, talcum, clay, lime carbonate etc. respectively with necessary amount, carry out mixingly with roll or Banbury, can make the bridging property rubber combination.In addition, as above-mentioned Synergist S-421 95, also can cooperate the rubber such as diene series rubber that dilute usefulness as required.

Diene series rubber as dilution usefulness, for example, can list natural rubber (NR), polyisoprene rubber (IR), letex polymerization styrene butadiene copolymer rubber (SBR), the random SBR of solution polymerization (combined styrene 1～50 weight %, 1 of divinyl part, 2-key amount 8～80%), high trans SBR (the trans key amount 70～95% of divinyl part), low-cis-polybutadiene rubber (BR), high-cis BR, high trans BR (the trans key amount 70～95% of divinyl part), the styrene-isoprene copolymer rubber, butadiene-isoprene copolymer glue, styrene butadiene-isoprene copolymer rubber, the styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubbers etc. can be selected aptly according to desired characteristic.These diene series rubbers can be used alone or in combination of two or more kinds separately.In addition, rubber constituent liquid can contain polyether rubber, viton, silicon rubber, ethylene-propylene-elastoprene and the urethanes etc. of acrylic rubber, epichloro hydrin rubber etc.

According to the present invention, contain silane coupling agent if make in the bridging property rubber combination,, be preferred therefore then owing to the low oil consumption of the crosslinked diolefin series cross-linked rubber that obtains, add epistasis and wear resistant can further improve.

As silane coupling agent; for example; can list vinyltriethoxysilane, β-(3; 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, two (3-(triethoxysilyl) propyl group) four thioethers, two (3-(triethoxysilyl) propyl group) disulfide etc., and the special four thioether classes of opening γ-trimethoxy-silylpropyl dimethyl thiocarbamoyl four thioethers of putting down in writing in the flat 6-248116 communique, γ-trimethoxy-silylpropyl benzothiazolyl four thioethers etc. etc.Because the incipient scorch when having avoided mixing, therefore the sulphur that preferably contains in the silane coupling agent of a part is below 4.

These silane coupling agents can use separately, perhaps also can will be used in combination more than 2 kinds.With respect to silica 1 00 weight part, the use level of silane coupling agent is preferably 0.1～20 weight part, and more preferably 0.5～15 weight part most preferably is 1～10 weight part.

As above-mentioned carbon black, can list carbon blacks such as furnace treated black, acetylene black, thermal black, thermally oxidized black, graphite.Wherein preferred furnace treated black particularly, can list SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, FEF etc.

Above-mentioned carbon black can use separately, perhaps also can will be used in combination more than 2 kinds.With respect to rubber 100 weight parts, below 150 weight parts, the total amount of carbon black and silicon-dioxide is preferably 20～200 weight parts to the sooty use level usually.

There is no particular limitation for above-mentioned sooty BET specific surface area, is preferably 30～200m ²/ g, more preferably 50～150m ²/ g most preferably is 70～140m ²/ g.In addition, above-mentioned sooty oil number is preferably 30～300ml/100g, and more preferably 50～200ml/100g most preferably is 80～160ml/100g.

As linking agent, can list sulphur such as powder sulphur, sedimentation sulphur, colloid sulphur, insoluble sulphur, high dispersive sulphur; Organo-peroxides such as halogenation such as sulfur monochloride, sulfur dichloride sulphur, dicumyl peroxide, di-t-butyl peroxide; P-benzoqui(o)none dioxime, right, right-benzoquinones dioximes such as dibenzoyl benzoquinones dioxime; Triethylenetetramine (TETA), hexamethylene-diamine carbamate, 4,4 '-organic polyamine compounds such as methylene radical two Ortho-Chloro anilines, have the alkyl phenol resin of methylol etc., wherein preferably sulphur, especially preferably powder sulphur.These linking agents can use separately, perhaps also can will be used in combination more than 2 kinds.

With respect to diene series rubber composition 100 weight parts, the use level of linking agent is preferably 0.1～15 weight part, and more preferably 0.3～10 weight part is preferably 0.5～5 weight part especially.When linking agent is in this scope, oil consumption and to add epistasis all good.

As crosslinking accelerator, can list N-cyclohexyl 2-[4-morpholinodithio base sulfinyl amine, the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine, N-oxo ethylidene-2-[4-morpholinodithio sulfinyl amine, N, N-di-isopropyl-sulfinyl amines such as 2-[4-morpholinodithio sulfinyl amine are crosslinking accelerator; Guanidines such as diphenylguanidine, two adjacent three guanidines, adjacent three guanidines are crosslinking accelerator; Thiocarbamides such as diethyl thiourea are crosslinking accelerator; Thiazoles such as 2-mercaptobenzothiazole, dibenzo dithiazole base thioether, 2-mercaptobenzothiazole zinc salt are crosslinking accelerator; Thiurams such as tetra methylthiuram one thioether, tetra methylthiuram disulfide are crosslinking accelerator; Diethyldithiocar bamic acid such as Sodium dimethyldithiocarbamate 40min, zinc diethyldithiocarbamate is a crosslinking accelerator; Xanthogenic acid such as zinc isopropyl xanthate are the crosslinking accelerator of crosslinking accelerator etc.

These crosslinking accelerators can use separately, perhaps also can will be used in combination more than 2 kinds, and especially preferably containing sulfinyl amine is those crosslinking accelerators of crosslinking accelerator.

With respect to diene series rubber composition 100 weight parts, the use level of crosslinking accelerator is preferably 0.1～15 weight part, and more preferably 0.3～10 weight part is preferably 0.5～5 weight part especially.

There is no particular limitation in agent as crosslinking activity, can use senior lipid acid such as stearic acid or zinc oxide etc.As zinc oxide, preferably use the high granularity of surfactivity the sort of below 5 μ m, can list active zinc flower that granularity is 0.05～0.2 μ m and the zinc oxide of 0.3～1 μ m.In addition, also can use with amine is that dispersion agent or wetting agent carried out surface-treated zinc oxide.These crosslinking activity agent can be used separately, perhaps also can use merging more than 2 kinds.

The cooperation ratio of crosslinking activity agent can be selected aptly according to the kind of crosslinking activity agent.With respect to diene series rubber composition 100 weight parts, the use level of higher fatty acid is preferably 0.05～15 weight part, and more preferably 0.1～10 weight part is preferably 0.5～5 weight part especially.With respect to diene series rubber composition 100 weight parts, the use level of zinc oxide is preferably 0.05～10 weight part, and more preferably 0.1～5 weight part is preferably 0.5～3 weight part especially.

As other Synergist S-421 95, can list glycol ether, polyoxyethylene glycol, the agent of silicone oil isoreactivity; Weighting agents such as clay, aluminium hydroxide, starch; Wax etc.

The compound method of bridging property rubber combination of the present invention is without any restriction, for example, after the diene rubber composition that will obtain in the Synergist S-421 95 linking agent and the crosslinking accelerator and the present invention is mixing, in this mixing thing, be mixed into linking agent and crosslinking accelerator, can make the bridging property rubber combination.The Synergist S-421 95 except linking agent and crosslinking accelerator and the mixing time of diene rubber composition are preferably 30 seconds～30 minutes.In addition, melting temperature is preferably 80～200 ℃, more preferably 100～190 ℃, is preferably 140～180 ℃ scope especially.Linking agent cooperates with crosslinking accelerator, is being cooled to below 100 ℃, is preferably carrying out after below 80 ℃ again usually.

With respect to bridging property rubber combination of the present invention, in the occasion that further contains silane coupling agent, the intermiscibility of silicon-dioxide and rubber further improves, and compares with the composition that does not cooperate silane coupling agent, and the amount of bound rubber increases.But the characteristic of making the occasion of bridging property rubber combination by this bound rubber is far superior to only use silane coupling agent to solidify altogether and the diene rubber composition that forms equal extent bound rubber amount.

This can contain because the difference on effect that bound rubber caused that the existence of cationic high-molecular generates is confirmed by diene rubber composition of the present invention.

Among the present invention, for the above-mentioned bridging property rubber combination that contains behind the silane coupling agent, the use level of preferred adjustment silane coupling agent, melting temperature, mixing time etc., so that be 0.30～1.20 with respect to the amount (g/ silica 1 g) of the bound rubber of silica 1 g, be preferably 0.35～1.10, more preferably 0.40～1.00.

(diolefin series cross-linked rubber)

According to the present invention, above-mentioned bridging property rubber combination is shaped carries out after the processing crosslinked and obtain the method for diolefin series cross-linked rubber there is no particular limitation, as long as select according to the proterties of cross-linking agent, size etc.For example, can in mould, fill bridging property rubber combination and heating, when being shaped, carry out crosslinkedly thus, also can carry out the uncrosslinked property rubber combination heating that is shaped in advance crosslinked.Crosslinking temperature is preferably 120 ℃～200 ℃, and more preferably 140～180 ℃, crosslinking time was generally about 1～120 minute.

(manufacture method of diene rubber composition)

Though the method for making diene rubber composition of the present invention is without any restriction, if but disclose the best way, can list silicon-dioxide is mixed in water with cationic high-molecular, after obtaining aqueous liquid dispersion, this aqueous liquid dispersion is mixed with the latex (rubber latex) of the diene series rubber with above-mentioned molecular weight distribution, silicon-dioxide and rubber are solidified altogether, dewater also dry and method that obtain.

There is no particular limitation for rubber concentrations in the above-mentioned rubber latex, as long as suit to set according to purpose, purposes.Usually be advisable with the scope of 5～80 weight %.In addition, above-mentioned rubber latex can use the rubber latex that carries out stabilization treatment through anionic emulsifier, nonionic emulsifier, cationic emulsifier etc.Wherein, the preferred rubber latex that carries out stabilization treatment through anionic emulsifier that uses.That is,, obtain a kind of like this rubber combination easily by the reaction of cationic high-molecular and anionic emulsifier, wherein, part or all of rubber and silicon-dioxide solidify altogether, and silicon-dioxide is evenly filled, and to have with respect to silicon-dioxide be the bound rubber of optimum quantity.

As above-mentioned anionic emulsifier, for example, preferred hard soap and/or the lemongrass hydrochlorate of carbonatoms more than 10.As concrete example, can list the sylvite or the sodium salt of lipid acid such as capric acid, lauric acid, tetradecanoic acid, palmitinic acid, oleic acid, stearic acid.

In addition, the silica concentration in the aqueous dispersions of above-mentioned silicon-dioxide is suitably 1～40 weight % usually.

Especially, above-mentioned silicon-dioxide preferably uses not the silicon-dioxide drying that will obtain by the neutralization reaction of silicate base and acid, but directly makes it be scattered in the water and the aqueous liquid dispersion through adjusting with the form of slurries shape or wet cake shape.

The blending means of the aqueous liquid dispersion of above-mentioned rubber latex, silicon-dioxide has no particular limits, and the aqueous dispersions of silicon-dioxide can be added in the rubber latex, also rubber latex can be added in the aqueous dispersions of silicon-dioxide.In addition, also rubber latex can be mixed simultaneously with the aqueous dispersions of silicon-dioxide.

Should illustrate, solidifying altogether of above-mentioned diene series rubber and silicon-dioxide, can make by cationic high-molecular be used for solidifying of rubber finished, also can be as required, use mineral acids such as those sulfuric acid that can make solidifying of rubber and finish, phosphoric acid, hydrochloric acid; Organic acids such as formic acid, acetate, butyric acid; The acid of Lewis acids such as Tai-Ace S 150 etc., the salt of sodium-chlor, calcium chloride etc.

(inflation method of bound rubber)

According to above-mentioned manufacture method, adjust the method for the amount of the bound rubber in the resulting diene rubber composition, have no particular limits, as to the influential representational key element of bound rubber, the specific surface area and the particle diameter of employed silicon-dioxide arranged.That is, the specific surface area of employed silicon-dioxide is high more, and particle diameter is more little, and the growing amount of bound rubber just increases more.Therefore, as long as adjust the specific surface area of employed silicon-dioxide and particle diameter etc. aptly so that the amount of bound rubber enters above-mentioned scope.Particularly, as mentioned above, preferred sedimentation silicon-dioxide, its specific surface area (S _BET) as mentioned above, be preferably 70～300m ²/ g, more preferably 80～280m ²/ g, most preferably 90～260m ²/ g.

In addition, as median size, can adopt 1～40 μ m (it is following not contain 1 μ m), the scope of preferred 10～30 μ m at the above-mentioned silicon-dioxide that uses when solidifying altogether.

The particle diameter of the silicon-dioxide that uses when solidifying altogether is adjusted to the operation of above-mentioned scope, so long as got final product before solidifying altogether.And its inflation method is not particularly limited, and can use known method.For example, can wait the suitable dry type comminuting method that is adjusted to target grain size by using injector-type mill, ball mill, Na ラ ミ Le, micromill [micromill], perhaps also can wait the suitable case of wet attrition method that is adjusted to target grain size by using dispersion machine, homogenizer, high-pressure homogenizer, colloidal mill.In addition, adopt the case of wet attrition method to adjust the occasion of silicon-dioxide particle diameter, also can in water, organic solvent or rubber latex or in their mixed emulsion, adjust.

In addition, as to influential other the representational key elements of bound rubber amount, can list the usage quantity of cationic high-molecular.That is, the usage quantity of cationic high-molecular increases more, and the growing amount of bound rubber just increases more.Specifically, as mentioned above, with respect to silica 1 00 weight part, cationic high-molecular is preferably 0.1～7.5 weight part.Especially, because above-mentioned reason, when the specific surface area that silicon-dioxide is recorded by above-mentioned CTAB (unit: m ²/ g) as S, above-mentioned cationic high-molecular with respect to the use level of above-mentioned silica 1 00 weight part (unit: during weight part) as c, preferably with above-mentioned cationic high-molecular according to its usage quantity of the conditional decision that satisfies following relational expression.

27≤(S/c)≤70

According to the present invention, in the occasion of using through the diene series rubber latex of anionic emulsifier stabilization, to maintain on one side in 5～11 the scope at the pH in the reaction system that the aqueous liquid dispersion that makes this rubber latex and silicon-dioxide and cationic high-molecular reacts, solidify altogether on one side, the particle diameter of the co-coagulate that obtains like this is big, easily carry out filtration described later, exsiccant operation, therefore comparatively desirable.

Should illustrate that among the present invention, reaction system is meant the aqueous liquid dispersion of silicon-dioxide, cationic high-molecular and the system of the state that mixes through the diene series rubber latex of anionic emulsifier stabilization.

Present inventors have carried out research repeatedly for the mechanism of the common coagulation reaction of the aqueous liquid dispersion of diene series rubber latex, silicon-dioxide and the cationic high-molecular of process anionic emulsifier stabilization, found that the pH value in the reaction system of solidifying altogether has a significant impact the particle diameter of the co-coagulate that generated.That is, if to make above-mentioned reaction system be pH less than 5 acidity, then the particle diameter of the co-coagulate that is generated is little, and maintains more than 5 by the pH that makes reaction system, and particularly more than 6, the particle diameter of the co-coagulate that is generated increases, and filterableness significantly improves.And, in the co-coagulate that obtains, can obtain the homodisperse diene rubber composition of silicon-dioxide.

Past, the example that the common coagulation reaction of above-mentioned reaction system is carried out more than pH5 as described above not, this experience is at first found by the present invention.

On the one hand, dissolve again, and in order to carry out common coagulation reaction effectively, the upper limit of the pH value of above-mentioned reaction system is preferably too not high, wishes below pH11, preferably below pH10 in order to prevent silicon-dioxide.

According to the present invention, above-mentioned is that 5～11 methods of solidifying altogether have no particular limits while the pH value of keeping reaction system, but, if desired, preferably in the aqueous liquid dispersion of silicon-dioxide and cationic high-molecular, add acid or alkali, make its pH value reach above-mentioned scope, under agitation slowly add method then through the diene series rubber latex of this anionic emulsifier stabilization; The aqueous liquid dispersion of silicon-dioxide and cationic high-molecular is added to through the scheme in the diene series rubber latex of anionic emulsifier stabilization while maintaining above-mentioned scope.In addition, in the occasion of considering continuous solidification technology, carry out the blended scheme simultaneously while preferably will maintain above-mentioned scope through the aqueous liquid dispersion of the diene series rubber latex of anionic emulsifier stabilization and silicon-dioxide and cationic high-molecular.Wherein, to carry out the blended scheme simultaneously while maintaining above-mentioned scope through the diene series rubber latex of anionic emulsifier stabilization and the aqueous liquid dispersion of silicon-dioxide and cationic high-molecular, owing to can be easily the pH value of reaction system be adjusted into necessarily, thereby the particle diameter that makes the co-coagulate of generation becomes evenly, is most preferred therefore.

When the pH at above-mentioned initial stage adjusted, the pH value of often employed diene series rubber latex through the anionic emulsifier stabilization was above above-mentioned scope, but so long as this pH, the carrying out that solidifies is also slow altogether, and the state that temporarily exceeds the upper limit is allowed.

In addition, in the above-mentioned reaction system, in the pH value can being maintained 5～11 scope, merge and use above-mentioned acid or salt, also can solidify altogether.Especially, the aqueous liquid dispersion of silicon-dioxide and cationic high-molecular is added to scheme in the above-mentioned diene series rubber latex while the scope of keeping above-mentioned pH, with the aqueous liquid dispersion of diene series rubber latex and silicon-dioxide and cationic high-molecular simultaneously in the blended scheme, merge and use above-mentioned acid or salt to solidify altogether, because the particle diameter of the co-coagulate that is generated increases, filterableness improves, and is preferred therefore.Make the pH that solidifies when finishing be preferably 5.0～8.0, more preferably 5.0～7.5, most preferably be 5.0～7.0.

Among the present invention, the temperature of above-mentioned reaction system has no particular limits, and is preferably 20～80 ℃.In addition, those methods of using common diverting devices such as water screw, dispersing and mixing machine, homogenizer to carry out of the general preferred employing of the mixing of reaction system.

(aftertreatment)

In addition, have no particular limits, as long as suitablely use the general method of using for each operations such as the filtration of the solid substance that solidifies the diene series rubber that obtains and silicon-dioxide altogether (hereinafter referred to as wet grume (Network ラ system)), washing, dehydration, dryings.Can adopt a kind of like this method, promptly, the grume that will wet separates with liquid component (hereinafter referred to as slurries (セ ラ system)), after the wet grume washing that obtain, filtering, with crowded branches that anhydrates such as extrusion machines to dewater, be ground into granular after, carry out drying with extruding drying machine, hot air dryer etc., be configured as particulate state or bulk.In addition, also can not separate wet grume and slurries, by spraying drying, the grume that will wet is configured as Powdered.

Embodiment

In order to be described more specifically the present invention, below enumerate embodiment and comparative example describes, but the present invention is not subjected to the qualification of these embodiment.Should illustrate that the various rerum naturas in embodiment and the comparative example adopt following method to measure.In addition, `` ``

(1) median size of silicon-dioxide

Using particle size distribution device (コ one Le one society's system, the コ one Le one LS-230) mensuration of scattering of light diffraction-type is the meta particle diameter of benchmark with the volume, should be worth as median size.

(2) specific surface area

Adopt the nitrogen adsorption method to come measurement the specific area (S _BET)

Silica wetcake is put into moisture eliminator (120 ℃) carry out drying, then, use the ア サ Star プ 2010 of マ イ Network ロ メ リ テ イ Network ス society system, measure the nitrogen adsorption amount, adopt the value of 1 method at relative pressure 0.2 place.

Adopt cetyl trimethylammonium bromide (CTAB) absorption to come measurement the specific area (S _CTAB)

Silica wetcake is put into moisture eliminator (120 ℃) carry out drying, then, implement according to the method for ASTM D3765-92 record.But the method for ASTM D3765-92 record is to be used to measure sooty S _CTABMethod, present embodiment is to its method of some improvement in addition.That is, do not use ITRB (83.0m as the carbon standard sample ²/ g), adjust the CTAB reference liquid in addition, carry out the dioctylis sulfosuccinas natricus standardizing of solution thus, making per 1 molecule of CTAB is 35 square angstroms with respect to the absorption sectional area of silica sphere, calculates specific surface area by the adsorptive capacity of CTAB.This is considered to because carbon black is different with the condition of surface of silicon-dioxide, even same specific surface area, the adsorptive capacity of CTAB also has different causes.

(3) (oil number)

Obtain according to JIS K6220.

(4) the styrene units amount in the multipolymer:

Measure according to JIS K6383 (index method).

(5) mooney viscosity

(it is made to go up the island making, VR-103ST), measures under 130 ℃ to use mooney's viscosimeter.

(6) silicon-dioxide containing ratio

Use apparatus for thermal analysis TG/DTA (Seiko electronic industry system TG/DTA320), the weight decrement when measuring dry the sample retained percentage after the thermolysis and temperature in air and reaching 150 ℃ uses following formula calculating.Among the embodiment, in amount (weight part) the back record that is converted into respect to rubber 100 weight parts.Condition determination is, in air, 20 ℃/min of heat-up rate arrives 600 ℃ of temperature, and the hold-time under 600 ℃ is 20 minutes.

Silicon-dioxide containing ratio (weight %)=

Combustion residue percentage/[100-(the weight decrement when reaching 150 ℃)] * 100

(7) with respect to the amount of the rubber constituent (bound rubber) of the toluene insoluble of silica 1 g

Dry sample 0.2g is cut into the size of 2mm about square, join in the basket made from the stainless steel wire netting of 280 orders (mesh 53 μ m), impregnated in the 60ml toluene, under 23 ℃, left standstill 72 hours.After 72 hours, take out from basket, use washing with acetone, 40 ℃ of following vacuum-dryings 12 hours, the toluene insoluble composition was obtained in weighing.The rubber constituent amount (g/ silica 1 g) that is insoluble in the toluene with respect to silica 1 g is calculated with following formula.

The rubber constituent amount (g/ silica 1 g) in the toluene of being insoluble to respect to silica 1 g

＝

[(toluene insoluble is separated the silica volume (g) in composition (g)-sample)/

Silica volume in the sample (g)]

Should illustrate that the silica volume in the said sample is that basic calculation goes out with the numerical value of calculating by above-mentioned (6) silicon-dioxide containing ratio.In addition, in the bridging property diene rubber composition, toluene insoluble is separated the solid substance beyond the silicon-dioxide such as often having zinc oxide in the composition.In this occasion, calculate after will from the toluene insoluble composition, deducting by the silicon-dioxide solid substance amount in addition that adding proportion is obtained.

(8) 300% modulus, tensile strength, elongation

Tensile stress test method(s) according to JIS K6253 is measured.

(9) wear resistant

Use ア Network ロ Application formula wear testing machine, the decrement by the weight after the weight after the preparation friction 1000 times and the main friction 1000 times calculates the abrasion performance index.This abrasion performance exponential value is big more, and the expression abradability is good more.

(10) road surface tack (the tan δ under 0 ℃)

Use the Measurement of Dynamic Viscoelasticity device ARES of レ オ メ ト リ Star Network ス society system, under the condition of distortion 0.2%, frequency 15Hz, the tan δ under measuring 0 ℃.The value of this tan δ (0 ℃) is big more, and expression road surface tack is good more.

(11) oil consumption (the tan δ under 60 ℃)

Use the Measurement of Dynamic Viscoelasticity device ARES of レ オ メ ト リ Star Network ス society system, under the condition of distortion 0.2%, frequency 15Hz, the tan δ under measuring 60 ℃.The value of this tan δ (0 ℃) is more little, and the low oil consumption of expression is good more.

(12) molecular weight data

The molecular weight data of polymkeric substance, (GPC) measures with gel permeation chromatograph, obtains the weight-average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) that convert by polystyrene standard.GPC is HLC-8020 (a Dong Caoshe system), as pillar, uses two pillars that link to each other and form of GMH-HR-H (Dong Caoshe system), detects and uses differential refractometer RI-8020 (Dong Caoshe system) to carry out.

(13) be total to curdled appearance

Can't see silicon-dioxide fully in the slurries after solidifying altogether and be transparence be, can see that the △ that is that some silicon-dioxide suspend is arranged, can see considerable silicon-dioxide suspension and for opaque for *.

(14) filterableness

To contain the coagulative aqueous solution and put in the screen cloth of mesh 212 μ m, and measure respectively and sieve last, undersized dry weight, obtain the weight percent that passes through.This value is more little, and the size of expression co-coagulate is big more, and yield rate is high more.

In addition, measure when using quantitative paper (ア De バ Application テ Star Network Japan (strain) system, quantitative paper No.5A) to filter the needed time (filtration time: second) when filtering.

(Production Example 1 of rubber latex)

In the voltage-resistant reactor that has stirrer, add 200 parts of deionized waters, 1.5 parts of citronellic acid soaps, 2.1 parts of fatty acid soaps, as 0.20 part of 72 parts of monomeric 1,3-butadienes, 28 parts of vinylbenzene and uncle's lauryl mercaptan.Temperature of reactor is made as 10 ℃, in reactor, adds as 0.03 part in 0.04 part of 0.03 part of diisopropylbenzenehydroperoxide, the rongalite of polymerization starter and 0.01 part of sodium ethylene diamine tetracetate and ferric sulfate, beginning polymerization.When polymerisation conversion reaches 45%, add 0.05 part of uncle's lauryl mercaptan, make it continue reaction.When polymerisation conversion reaches 70%, add 0.05 part of diethyl hydroxylamine, make its stopped reaction.

After adopting wet distillation that unreacted monomer is gone out, with respect to polymkeric substance 100 weight parts, the emulsion aqueous solution with 30 weight % adds as ageing-resistant octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) 0.8 part of propionic ester and 2,0.12 part in two (n-octyl the sulphomethyl)-6-cresols of 4-obtain the polymer latex (hereinafter referred to as La1) of solid concentration 24 weight %.

Its part is taken out, with sulfuric acid be adjusted to pH3～5 on one side, with sodium-chlor polymer latex is solidified under 50 ℃ on one side, obtain wet sticking blocky polymkeric substance.With the hot air dryer drying of this wet grume, obtain solid shape rubber (hereinafter referred to as Ru1) with 80 ℃.The vinylbenzene amount 23.6 weight % of the rubber that obtains, mooney viscosity is 52.In addition, molecular weight is 415,000, and molecular weight distribution is 3.74.The solid shape rubber (Ru1) that obtains is used for embodiment 4,5, comparative example 1,6 and 10.

(Production Example 2 of rubber latex)

In the voltage-resistant reactor that has stirrer, add 200 parts of deionized waters, 1.5 parts of citronellic acid soaps, 2.1 parts of fatty acid soaps, as 0.09 part of 57.5 parts of monomeric 1,3-butadienes, 42.5 parts of vinylbenzene and uncle's lauryl mercaptan.Temperature of reactor is made as 10 ℃, in reactor, add as 0.02 part in 0.06 part of 0.1 part of diisopropylbenzenehydroperoxide, the rongalite of polymerization starter and 0.014 part of sodium ethylene diamine tetracetate and ferric sulfate, the beginning polymerization. when polymerisation conversion reaches 45%, add 0.05 part of uncle's lauryl mercaptan, make it continue reaction.When polymerisation conversion reaches 70%, add 0.05 part of diethyl hydroxylamine, make its stopped reaction.

After adopting wet distillation that unreacted monomer is removed, with respect to polymkeric substance 100 weight parts, with the 60 weight % emulsion aqueous solution, interpolation is as ageing-resistant N-(1, the 3-dimethylbutyl)-and 0.21 part of N '-diphenyl-para-phenylene diamine and 2,2,4-trimethylammonium-1,0.14 part of 2-dihydroquinoline obtains the polymer latex (hereinafter referred to as La2) of solid concentration 24 weight %.Its part is taken out, with sulfuric acid be adjusted to pH3～5 on one side, with sodium-chlor polymer latex is solidified under 50 ℃ on one side, obtain wet sticking blocky polymkeric substance.With the hot air dryer drying of this wet grume, obtain solid shape rubber with 80 ℃.The vinylbenzene amount of the rubber that obtains is 35.0 weight %, and mooney viscosity is 150.In addition, molecular weight is 892,000, and molecular weight distribution is 3.80.

The part of above-mentioned polymer latex (hereinafter referred to as La2) is taken out, with respect to polymkeric substance 100 weight parts in polymer latex Ruzhong, add 37.5 parts of aqueous emulsions that form 66 amount amount % as the Enerthene1849 (Block リ テ イ Star シ ユ ペ ト ロ リ ア system society system) of extending oil with fatty acid soaps.Then, on one side with the sulfuric acid adjustment reaching pH3～5, with sodium-chlor the polymer latex that contains extending oil is solidified under 60 ℃ on one side, obtain wet sticking blocky polymkeric substance.This wet grume is dry in 80 ℃ hot air dryer, obtain solid shape rubber (Ru2).The mooney viscosity of the rubber that obtains is 49.The solid shape rubber (Ru2) that obtains is used for comparative example 9.

(Production Example 1 of silicon-dioxide)

To the 1m that has the temperature regulation machine ³Add sodium silicate aqueous solution (SiO in the stainless steel reaction vessel ₂Concentration: 10g/L, mol ratio: SiO ₂/ Na ₂O=3.41) 230L is warming up to 85 ℃.Then, spend 120 minutes and add 22 weight % sulfuric acid 73L and sodium silicate aqueous solution (SiO simultaneously ₂Concentration: 90g/L, mol ratio: SiO ₂/ Na ₂O=3.41) 440L.After the slaking 10 minutes, spend 15 minutes and add 22 weight % sulfuric acid 16L.Reacting liquid temperature is remained on 85 ℃, on one side often stirring reaction liquid carry out above-mentioned reaction on one side, the pH that finally obtains reaction solution is 3.2 silica slurry.It is used the pressure filter press filtration, washing, filter, obtain the silicon-dioxide solid substance and be 23% silica wetcake (A).

The part of the silica wetcake (A) that obtains is dry, the BET specific surface area (S of the SiO 2 powder that obtains (a) _BET) be 201m ²/ g, CTAB specific surface area (S _CTAB) be 190m ²/ g, oil number is 210ml/100g.The SiO 2 powder that obtains (a) is used for embodiment 8, comparative example 1 and 2.

(Production Example 2 of silicon-dioxide)

To the 1m that has the temperature regulation machine ³Add sodium silicate aqueous solution (SiO in the stainless steel reaction vessel ₂Concentration: 10g/L, mol ratio: SiO ₂/ Na ₂O=3.41) 200L is warming up to 95 ℃.Then, spend 140 minutes and add 22 weight % sulfuric acid 77L and sodium silicate aqueous solution (SiO simultaneously ₂Concentration: 90g/L, mol ratio: SiO ₂/ Na ₂O=3.41) 455L.After the slaking 10 minutes, spend 15 minutes and add 22 weight % sulfuric acid 16L.Reacting liquid temperature is remained on 95 ℃, on one side often stirring reaction liquid carry out above-mentioned reaction on one side, the pH that finally obtains reaction solution is 3.2 silica slurry.It is used the pressure filter press filtration, and washing, filtration obtain the silica wetcake that the silicon-dioxide solid substance is 25 weight % (B).

The part of the silica wetcake (B) that obtains is dry, the BET specific surface area (S of the SiO 2 powder that obtains (b) _BET) be 121m ²/ g, CTAB specific surface area (S _CrAB) be 110m ²/ g, oil number is 170ml/100g.The SiO 2 powder that obtains (b) is used for comparative example 6 and 9.

(Production Example 3 of silicon-dioxide)

To the 1m that has the temperature regulation machine ³Reaction vessel in add sodium silicate aqueous solution (SiO ₂Concentration: 10g/L, mol ratio: SiO ₂/ Na ₂O=3.41) 158L is warming up to 95 ℃.Then, spend 210 minutes and add 22 weight % sulfuric acid 90L and sodium silicate aqueous solution (SiO simultaneously ₂Concentration: 90g/L, mol ratio: SiO ₂/ Na ₂O=3.41) 535L.After the slaking 10 minutes, spend 40 minutes and add 22 weight % sulfuric acid 17L.Reacting liquid temperature is remained on 95 ℃, on one side often stirring reaction liquid carry out above-mentioned reaction on one side, the pH that finally obtains reaction solution is 3.1 silica slurry.It with pressure filter washing, filtration, is obtained the silica wetcake that the silicon-dioxide solid substance is 28 weight % (C).

The part of the silica wetcake (C) that obtains is dry, the BET specific surface area (S of the SiO 2 powder that obtains (c) _BET) be 92m ²/ g, CTAB specific surface area (S _CTAB) be 85m ²/ g, oil number is 160ml/100g.The SiO 2 powder that obtains (c) is used for comparative example 10.

(the formulation example I of the aqueous dispersions of silicon-dioxide～XIII)

Silica wetcake (A)～(C) or SiO 2 powder (a) that aforesaid method is obtained mix with cationic high-molecular and the pure water shown in table 1 and 2, make the silica concentration in the aqueous dispersions become 15 weight %, in addition, make cationic high-molecular become the ratio shown in the table 1,2 with respect to the ratio (weight part) of silica 1 00 weight part, use homogenizer, silica wetcake or SiO 2 powder are mixed while pulverizing, obtain containing the silica aqueous dispersion (I)～(XIII) of cationic high-molecular.Should illustrate that silica aqueous dispersion (VII) and (XIII) handling the back with homogenizer and then using high-pressure homogenizer is carried out 1 time and handled under processing pressure 80MPa.The median size of the silicon-dioxide in the aqueous dispersions of the silicon-dioxide that obtains, pH are shown in table 1 and 2.

＜embodiment 1 〉

600g mixes, stirs with pure water 2000g with silica aqueous dispersion (I), under agitation splashes into SBR latex (La1) 750g in this aqueous dispersions (I), and it is solidified altogether.Mixed pH is 7.3, and rubber solidifies fully.

After this coagulum filtration, washing, drying,, obtain flaky diene rubber composition 260g by roll.

The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 4.In addition, be 401,000 by the toluene solution Mw that obtain, that be dissolved in the rubber in the toluene that removes with vaporizer after bound rubber is measured, Mw/Mn is 3.69.

The diene rubber composition that obtains, add silane coupling agent (KBE-846 according to the use level shown in the table 3, SHIN-ETSU HANTOTAI's chemical industry system), paraffin wax, stearic acid, zinc oxide, antiaging agent (ノ Network ラ Star Network 6C, the emerging chemical industry of imperial palace society system), use Banbury (100 ℃ of mixing roll models of the smart machine-processed ラ ボ プ ラ ス ト ミ Le type of Japan B-250), mixing 2 minutes.Temperature during mixing the end is 140 ℃.Then, add vulcanization accelerator (ノ Network セ ラ one CZ, the emerging chemical industry of imperial palace society system) and sulphur,, use Banbury to descend mixing 1 minute, obtain the bridging property rubber combination at 70 ℃ to reach the use level shown in the table 3.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination that obtains is shown in Table 4.

The bridging property rubber combination that obtains was suppressed 15 minutes down at 160 ℃, crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 4.

＜embodiment 2 〉

600g mixes, stirs with pure water 2000g with silica aqueous dispersion (II), under agitation splashes into SBR latex (La1) 750g in this aqueous dispersions (II).Mixed pH is 8.0, because rubber does not solidify fully, solidifies so interpolation sulfuric acid is finished altogether it.The pH of this moment is 6.2.

After this coagulum filtration, washing, drying,, obtain flaky diene rubber composition 252g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 4.

The diene rubber composition that obtains adds various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 4.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 4.

＜embodiment 3 〉

Among the embodiment 1, except using silica aqueous dispersion (III) replacement (I), solidify operation similarly to Example 1 altogether.Mixed pH is 6.5, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying,, obtain flaky diene rubber composition 252g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 4.

The diene rubber composition that obtains adds various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 3.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 4.

＜embodiment 4 〉

Among the embodiment 1, except the use level that makes silica aqueous dispersion (I) is 1200g, solidify operation similarly to Example 1 altogether.Mixed pH is 6.1, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying,, obtain diene rubber composition 340g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 4.

The diene rubber composition that obtains adds solid shape rubber (Ru1) and various additive according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 4.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 4.

＜embodiment 5 〉

Among the embodiment 1, except the use level that makes silica dispersions (I) is 1800g, solidify operation similarly to Example 1 altogether.Mixed pH is 5.8, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying,, obtain diene rubber composition 440g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 4.

The diene rubber composition that obtains adds solid shape rubber (Ru1) and various additive according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 4.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 4.

＜embodiment 6 〉

Among the embodiment 1, except using silica aqueous dispersion (IV) replacement (I), solidify operation similarly to Example 1 altogether.Mixed pH is 7.8, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying,, obtain diene rubber composition 252g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 4.

The diene rubber composition that obtains adds various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 4.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 4.

＜embodiment 7 〉

Among the embodiment 1, except using silica aqueous dispersion (V) replacement (I), solidify operation similarly to Example 1 altogether.Mixed pH is 6.9, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying,, obtain diene rubber composition 252g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 4.

The diene rubber composition that obtains adds various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 4.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 4.

＜embodiment 8 〉

Among the embodiment 1, except using silica aqueous dispersion (VI) replacement (I), solidify operation similarly to Example 1 altogether.Mixed pH is 7.2, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying,, obtain diene rubber composition 252g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 4.

The diene rubber composition that obtains adds various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 4.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 4.

＜comparative example 1 〉

Cooperate solid shape rubber (Ru1), SiO 2 powder (a), various additive according to the use level shown in the table 3, carry out mixingly similarly to Example 1, obtain the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 5.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 5.

＜comparative example 2 〉

γ-sulfydryl propyl-triethoxysilicane (KBE-803, SHIN-ETSU HANTOTAI's chemical industry system) 7.5g, Virahol 5.0g and water 10g are mixed, behind the pH regulator to 4, at room temperature stir and became transparently in 20 minutes until mixed solution, make silane-water solution with Glacial acetic acid.

The silane-water solution that obtains is under agitation added to intermittently in the aqueous dispersions of the silicon-dioxide that blending dispersion has SiO 2 powder (a) 125g and pure water 800g, use 25% sodium hydroxide pH regulator to 7.7.Then, above-mentioned mixed solution remained under 70 ℃ the condition and stirred 4 hours, obtain the aqueous dispersions of the silicon-dioxide handled through silicoorganic compound.The median size of the silicon-dioxide in the aqueous dispersions of the silicon-dioxide that obtains is 20 μ m.

Then, in above-mentioned silica aqueous dispersion, mix SBR latex (La1) 1045g, under acidic conditions, it is solidified altogether with salt.

After this coagulum filtration, washing, drying,, obtain diene rubber composition 360g by roll.

The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 5.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 5.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 5.

＜comparative example 3 〉

Among the embodiment 1, except the use level that makes silica aqueous dispersion (I) is 3000g, solidify operation similarly to Example 1 altogether.Mixed pH is 5.2, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying, obtain diene rubber composition 600g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 5.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, attempts to carry out similarly to Example 1 mixing, but diene rubber composition is really up to the mark, can not be mixing.

＜comparative example 4 〉

Among the embodiment 1, except using silica aqueous dispersion (VII) replacement (I), solidify operation similarly to Example 1 altogether.Mixed pH is 4.8, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying, obtain diene rubber composition 252g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 5.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 5.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 5.

＜comparative example 5 〉

With the silica wetcake (A) that obtains as stated above, mix while use homogenizer to pulverize silica wetcake, so that the silica concentration in the aqueous dispersions becomes 15%, obtain silica aqueous dispersion.Silica aqueous dispersion 600g, pure water 2000g, SBR latex (La1) 750g are mixed stirring, under agitation in this mixed solution, splash into 10 weight % aqueous solution 27g of Epicholorohydrin dimethylamine multipolymer (molecular weight 240,000) lentamente, it is solidified altogether.Mixed pH is 7.3.

After this coagulum filtration, washing, drying,, obtain diene rubber composition 260g by roll.

The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 5.

The diene rubber composition that obtains carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 5.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 1.The results are shown in the table 5.

＜embodiment 9 〉

Among the embodiment 1, except using silica aqueous dispersion (VIII) replacement (I), solidify operation similarly to Example 1 altogether.Mixed pH is 7.5, and rubber solidifies fully.

Then, after this coagulum filtration, washing, drying,, obtain flaky diene rubber composition 252g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 6.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 6.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 6.

＜embodiment 10 〉

Silica aqueous dispersion (VIII) 600g with pure water 2000g dilution, is warming up to 50 ℃.Then, the pH of above-mentioned aqueous dispersions is remained on 3～5, under agitation splash into SBR latex (La1) 750g, it is solidified altogether, obtain the coagulum of diene rubber composition with 22 weight % sulfuric acid.Temperature maintenance when solidifying is at 50 ℃.

After this coagulum filtration, washing, drying, obtain diene rubber composition 260g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 6.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 6.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 6.

＜embodiment 11 〉

SBR latex (La1) 750g with pure water 2000g dilution, is warming up to 50 ℃.Its pH is 9.8.Then, under agitation in the above-mentioned SBR latex (La1) that has diluted, add silica aqueous dispersion (VIII) 600g, make it generate the co-coagulate of silicon-dioxide and rubber.The pH of mixed solution is 7.5.Because the rubber in the SBR latex (La1) does not solidify fully, so then in above-mentioned mixed solution, add 10 weight % sulfuric acid, rubber is solidified fully, obtain the coagulum of diene rubber composition.The final pH of mixed solution is 6.5.

Should illustrate that the temperature maintenance of mixed solution is 50 ℃ following experimentizing.

After this coagulum filtration, washing, drying, obtain diene rubber composition 260g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 6.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 6.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 6.

＜embodiment 12 〉

SBR latex (La1) 750g with pure water 2000g dilution, is warming up to 50 ℃.Its pH is 9.8.Then, under agitation in the above-mentioned SBR latex (La1) that has diluted, add silica aqueous dispersion (IX) 600g, make it generate the co-coagulate of silicon-dioxide and rubber.The pH of mixed solution is 8.5.Because the rubber in the SBR latex (La1) does not solidify fully, so then in above-mentioned mixed solution, add 10% sulfuric acid, rubber is solidified fully, obtain the coagulum of diene rubber composition.The final pH of mixed solution is 6.5.Should illustrate that the temperature maintenance of mixed solution experimentizes under 50 ℃.

After this coagulum filtration, washing, drying, obtain exsiccant diene rubber composition 255g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 6.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 6.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 6.

＜embodiment 13 〉

SBR latex (La1) 750g with pure water 2000g dilution, is warming up to 50 ℃.Its pH is 9.8.Then, under agitation in the above-mentioned SBR latex (La1) that has diluted, add silica aqueous dispersion (X) 600g, make it generate the co-coagulate of silicon-dioxide and rubber.The pH of mixed solution is 7.5.Because the rubber in the SBR latex (La1) does not solidify fully, so then in above-mentioned mixed solution, add 10% sulfuric acid, rubber is solidified fully, obtain the coagulum of diene rubber composition.The final pH of mixed solution is 6.5.Should illustrate that the temperature maintenance of mixed solution experimentizes under 50 ℃.

After this coagulum filtration, washing, drying, obtain diene rubber composition 261g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 6.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 6.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 6.

＜embodiment 14 〉

SBR latex (La1) 750g with pure water 2000g dilution, is warming up to 50 ℃.Its pH is 9.8.Then, under agitation in the above-mentioned SBR latex (La1) that has diluted, add silica aqueous dispersion (XI) 600g, make it generate the co-coagulate of silicon-dioxide and rubber.The pH of mixed solution is 7.5.Because the rubber in the SBR latex (La1) does not solidify fully, so then in above-mentioned mixed solution, add 10% sulfuric acid, rubber is solidified fully, obtain the coagulum of diene rubber composition.The final pH of mixed solution is 6.5.Should illustrate that the temperature maintenance of mixed solution experimentizes under 50 ℃.

After this coagulum filtration, washing, drying, obtain diene rubber composition 251g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 6.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 6.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 6.

＜embodiment 15 〉

In being warming up to 50 ℃ pure water 2000g, under agitation add SBR latex (La1) 750g and silica aqueous dispersion (VIII) 600g simultaneously, make it generate the co-coagulate of silicon-dioxide and rubber.The pH of mixed solution is 7.5.Because the rubber in the SBR latex (La1) does not solidify fully, so then in above-mentioned mixed solution, add 10% sulfuric acid, rubber is solidified fully, obtain the coagulum of diene rubber composition.The final pH of mixed solution is 6.3.Should illustrate that the temperature maintenance of mixed solution experimentizes under 50 ℃.

After this coagulum filtration, washing, drying, obtain diene rubber composition 258g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 6.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 6.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 6.

＜comparative example 6 〉

Cooperate SBR (Ru1), SiO 2 powder (b), various additive according to the use level shown in the table 3, carry out mixingly similarly to Example 1, obtain the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 7.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 7.

＜comparative example 7 〉

Use the silica wetcake (B) that uses among the embodiment 9, use bromohexadecane base trimethyl ammonium so that silicon-dioxide becomes 3 weight parts, in addition, carry out same operation with the adjustment example of the aqueous dispersions of silicon-dioxide, obtain containing the silica aqueous dispersion (XIV) of bromohexadecane base trimethyl ammonium.The median size of the silicon-dioxide in the aqueous dispersions that obtains is 16 μ m.

Then, above-mentioned silica aqueous dispersion (XIV) 600g with pure water 2000g dilution, is warming up to 50 ℃.Then, the pH of above-mentioned aqueous dispersions is remained on 3～5, under agitation splash into SBR latex (La1) 750g, it is solidified altogether, obtain the coagulum of diene rubber composition with 22 weight % sulfuric acid.Temperature maintenance when solidifying experimentizes under 50 ℃.

After this coagulum filtration, washing, drying, obtain diene rubber composition 246g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 7.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 7.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 7.

＜comparative example 8 〉

Silica aqueous dispersion (XIII) 600g with pure water 2000g dilution, is warming up to 50 ℃.Then, the pH of above-mentioned aqueous dispersions is remained on 3～5, under agitation splash into SBR latex (La1) 750g, it is solidified altogether, obtain the coagulum of diene rubber composition with 22 weight % sulfuric acid.Temperature maintenance when solidifying experimentizes under 50 ℃.

After this coagulum filtration, washing, drying, obtain diene rubber composition 240g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 7.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 7.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 6.The results are shown in the table 7.

＜embodiment 16 〉

SBR latex (La2) 750g and extending oil Enerthene1849A (Block リ テ イ Star シ ユ ペ ト ロ リ ア system society system) are mixed with 66 weight % aqueous emulsion (hereinafter referred to as the fat liquor) 102g that fatty acid soaps forms, with pure water 2000g dilution, be warming up to 50 ℃ again.Its pH is 10.2.Then, in the above-mentioned SBR latex (La2) that contains extending oil that has diluted, under agitation add silica aqueous dispersion (XI) 840g, make it generate the co-coagulate of silicon-dioxide and rubber.The pH of mixed solution is 7.4.Because the rubber in the SBR latex (La2) does not solidify fully, so then in above-mentioned mixed solution, add 10% sulfuric acid, rubber is solidified fully, obtain the coagulum of diene rubber composition.The final pH of mixed solution is 6.3.Should illustrate that the temperature maintenance of mixed solution experimentizes under 50 ℃ condition.After this coagulum filtration, washing, drying, obtain diene rubber composition 365g.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the result of filterableness, the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 8.

In addition, the toluene solution that bound rubber is measured machine remove with vaporizer and in the toluene that obtains the Mw of dissolved rubber be 865,000, Mw/Mn is 3.75.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 8.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 9.The results are shown in the table 8.

＜comparative example 9 〉

Cooperate solid shape rubber (Ru2), SiO 2 powder (b), various additive according to the use level shown in the table 3, carry out mixingly similarly to Example 1, obtain the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 8.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 9.The results are shown in the table 8.

＜embodiment 17 〉

Among the embodiment 1, except using silica aqueous dispersion (XII) replacement (I), solidify operation similarly to Example 1 altogether.Mixed pH is 7.2, and rubber solidifies fully.Then, after this coagulum filtration, washing, drying,, obtain diene rubber composition 252g by roll.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the containing ratio of silicon-dioxide and the diene rubber composition is shown in Table 8.

The diene rubber composition that obtains cooperates various additives according to the use level shown in the table 3, carries out mixingly similarly to Example 1, obtains the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 8.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value is represented as 100 index with comparative example 10.The results are shown in the table 8.

＜comparative example 10 〉

Cooperate solid shape rubber (Ru1), SiO 2 powder (c), various additive according to the use level shown in the table 3, carry out mixingly similarly to Example 1, obtain the bridging property rubber combination.The rubber constituent amount that is insoluble to toluene (g/ silica 1 g) with respect to silica 1 g in the bridging property rubber combination is shown in Table 8.The bridging property rubber combination that obtains is carried out similarly to Example 1 crosslinked, make test film, measure each rerum natura.Measured value with comparative example 10 is represented as 100 index.The results are shown in the table 8.

The effect of invention

Be appreciated that from the above description diene rubber composition of the present invention, by by branch Wide diene series rubber, silica and the cationic high-molecular of son amount distribution consists of In the system, contain bound rubber with specific amount, make its shaping processability good and make The diene series cross-linked rubber that obtains with said composition has good tensile strength, abrasion performance Etc. rerum natura, particularly in the tire purposes, demonstrate and have low oil consumption and road surface tack concurrently Characteristic.

Industrial applicibility

Therefore, diene rubber composition of the present invention can utilize the various uses of above-mentioned characteristic In use, in each positions such as the tyre surface of tire, carcass, side walls, tyre bead section, or The rubber that the person utilizes at the bottom of flexible pipe, window frame, rubber strip, boots, Shockproof rubber, automotive department grade In the glue goods, and then, can also be as the tree of impact resistant polystyrene, ABS resin etc. The fat reinforcing rubber uses.

Wherein, be especially suitable for use as the tire parts, the tire tread that takes tire as low combustion is Particularly preferred.

Table 1

Table 2

Table 3

	Unit	Embodiment 1～3,6～15,17 comparative example 3～5 7,8	Embodiment 4	Embodiment 5	Embodiment 16	Comparative example 1,6,10	Comparative example 2	Comparative example 9
									Diene rubber composition	phr	150	100	83	207.5	-	150	-
Solid rubber	phr	-	50	67	-	100	-	137.5
									SiO 2 powder	phr	-	-	-	-	50	-	70
Silane coupling agent	phr	5	5	5	5	5	-	5
									Paraffin	phr	1	1	1	1	1	1	1
Stearic acid	phr	2	2	2	2	2	2	2
									Zinc oxide	phr	4	4	4	4	4	4	4
Age resister	phr	1	1	1	1	1	1	1
									Vulcanization accelerator	phr	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Sulphur	phr	2	2	2	2	2	2	2

Table 4

Table 5

Table 6

Table 7

Table 8

Claims (11)

1. diene rubber composition, it is characterized in that, comprising that the molecular weight distribution of the ratio of number-average molecular weight being represented with weight-average molecular weight is 1.1～30 diene series rubber 100 weight parts, silicon-dioxide 20～200 weight parts and cationic high-molecular, is 0.2～1g with respect to the amount of the rubber constituent that is insoluble to toluene of 1g silicon-dioxide.

2. the diene rubber composition described in the claim 1, wherein, the specific surface area (unit: m that silicon-dioxide adopts cetyl trimethylammonium bromide (CTAB) absorption method to record ²/ g) be 60～300m ²/ g.

3. the diene rubber composition described in the claim 1 or 2, wherein, being that the ratio of 0.1～7.5 weight part contains cationic high-molecular with respect to silica 1 00 weight part.

4. the diene rubber composition of claim 1～3 described in each is characterized in that, the specific surface area (unit: m that above-mentioned silicon-dioxide adopts cetyl trimethylammonium bromide (CTAB) absorption method to record ²/ g) be 70～200m ²/ g, when this specific surface area as S, above-mentioned cationic high-molecular with respect to the use level of above-mentioned silica 1 00 weight part (unit: during weight part) as c, cooperate above-mentioned cationic high-molecular according to the condition that satisfies following relational expression,

27≤(S/c)≤70。

5. the diene rubber composition of claim 1～4 described in each, it is characterized in that it is to make diene series rubber solidify the co-coagulate that obtains with silicon-dioxide by mixing through the cationic high-molecular that has uncle's amino or quaternary ammonium salt base on diene series rubber latex, silicon-dioxide and the high polymer main chain of anionic emulsifier stabilization or the side chain.

6. the diene rubber composition of claim 1～5 described in each is characterized in that the weight-average molecular weight of cationic high-molecular is 1000～1000000.

7. bridging property diene rubber composition, it is to cooperate linking agent and silane coupling agent to form in the diene rubber composition described in the claim 1～6.

8. diolefin series cross-linked rubber, it is to carry out crosslinked forming by the bridging property diene rubber composition described in the claim 7.

9. the manufacture method of a diene rubber composition, it is characterized in that, the cationic high-molecular that has uncle's amino or quaternary ammonium salt base on silicon-dioxide and high polymer main chain or the side chain is mixed in water, obtain aqueous liquid dispersion, be that 1.1～30 the diene series rubber latex through the anionic emulsifier stabilization mixes then with this aqueous liquid dispersion and the molecular weight distribution of the ratio of number-average molecular weight being represented with weight-average molecular weight, after silicon-dioxide and rubber are solidified altogether, with co-coagulate dehydration, drying.

10. the manufacture method of a silica-filled rubber is characterized in that, require in 9 at aforesaid right, on one side pH when aqueous liquid dispersion mixed with rubber latex maintain in 5～11 the scope, solidify altogether on one side.

11. the manufacture method of the silica-filled rubber described in the claim 9 wherein, is adjusted to 5～8 with the pH that finishes when solidifying altogether.